Ze-Xiang Yin, Yu-Dan Li, Yu-Huan Ye, Yuan Liu, Mian-Feng Li, Zi-Jun Yang, Xue-Rong Zheng, Hao-Zhi Wang, Yang Wang, Yi-Da Deng
{"title":"Sp/sp2 carbon ratio-driven high-throughput screening of electrocatalytic nitrogen reduction performance on transition metal single-atom catalysts","authors":"Ze-Xiang Yin, Yu-Dan Li, Yu-Huan Ye, Yuan Liu, Mian-Feng Li, Zi-Jun Yang, Xue-Rong Zheng, Hao-Zhi Wang, Yang Wang, Yi-Da Deng","doi":"10.1007/s12598-024-02836-0","DOIUrl":null,"url":null,"abstract":"<p>Single-atom catalysts (SACs) have been widely utilized in electrochemical nitrogen reduction reactions (NRR) due to their high atomic utilization and selectivity. Owing to the unique sp/sp<sup>2</sup> co-hybridization, graphyne materials can offer stable adsorption sites for single metal atoms. To investigate the influence of the sp/sp<sup>2</sup> hybrid carbon ratio on the electrocatalytic NRR performance of graphyne, a high-throughput screening of 81 catalysts, with 27 transition metals loaded on graphyne (GY1), graphdiyne (GY2), and graphtriyne (GY3), was conducted using first-principles calculations. The results of the screening revealed that Ti@GY3 exhibits the lowest energy barrier for the rate-determining step (0.32 eV) in NRR. Further, to explore the impact of different sp/sp<sup>2</sup>-hybridized carbon ratios on the catalytic activity of SACs, the mechanism of nitrogen (N<sub>2</sub>) adsorption, activation, and the comprehensive pathway of NRR on Ti@GY1, Ti@GY2, and Ti@GY3 was systematically investigated. It was found that the ratio of sp/sp<sup>2</sup>-hybridized carbon can significantly modulate the <i>d</i>-band center of the metal, thus affecting the energy barrier of the rate-determining step in NRR, decreasing from Ti@GY1 (0.59 eV) to Ti@GY2 (0.49 eV), and further to Ti@GY3 (0.32 eV). Additionally, the Hall conductance was found to increase with the bias voltage in the range of 0.4–1 V, as calculated by Nanodcal software, demonstrating an improvement in the conductivity of the SAC. In summary, this work provides theoretical guidance for modulating the electrocatalytic nitrogen reduction activity of SACs by varying the ratio of sp/sp<sup>2</sup> hybrid carbon, with Ti@GY3 showing potential as an excellent NRR catalyst.</p><h3 data-test=\"abstract-sub-heading\">Graphical abstract</h3>\n","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":null,"pages":null},"PeriodicalIF":9.6000,"publicationDate":"2024-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Rare Metals","FirstCategoryId":"88","ListUrlMain":"https://doi.org/10.1007/s12598-024-02836-0","RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"MATERIALS SCIENCE, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
Single-atom catalysts (SACs) have been widely utilized in electrochemical nitrogen reduction reactions (NRR) due to their high atomic utilization and selectivity. Owing to the unique sp/sp2 co-hybridization, graphyne materials can offer stable adsorption sites for single metal atoms. To investigate the influence of the sp/sp2 hybrid carbon ratio on the electrocatalytic NRR performance of graphyne, a high-throughput screening of 81 catalysts, with 27 transition metals loaded on graphyne (GY1), graphdiyne (GY2), and graphtriyne (GY3), was conducted using first-principles calculations. The results of the screening revealed that Ti@GY3 exhibits the lowest energy barrier for the rate-determining step (0.32 eV) in NRR. Further, to explore the impact of different sp/sp2-hybridized carbon ratios on the catalytic activity of SACs, the mechanism of nitrogen (N2) adsorption, activation, and the comprehensive pathway of NRR on Ti@GY1, Ti@GY2, and Ti@GY3 was systematically investigated. It was found that the ratio of sp/sp2-hybridized carbon can significantly modulate the d-band center of the metal, thus affecting the energy barrier of the rate-determining step in NRR, decreasing from Ti@GY1 (0.59 eV) to Ti@GY2 (0.49 eV), and further to Ti@GY3 (0.32 eV). Additionally, the Hall conductance was found to increase with the bias voltage in the range of 0.4–1 V, as calculated by Nanodcal software, demonstrating an improvement in the conductivity of the SAC. In summary, this work provides theoretical guidance for modulating the electrocatalytic nitrogen reduction activity of SACs by varying the ratio of sp/sp2 hybrid carbon, with Ti@GY3 showing potential as an excellent NRR catalyst.
期刊介绍:
Rare Metals is a monthly peer-reviewed journal published by the Nonferrous Metals Society of China. It serves as a platform for engineers and scientists to communicate and disseminate original research articles in the field of rare metals. The journal focuses on a wide range of topics including metallurgy, processing, and determination of rare metals. Additionally, it showcases the application of rare metals in advanced materials such as superconductors, semiconductors, composites, and ceramics.